Hair coloring method using a peroxydiphosphate oxidant

ABSTRACT

Hair and other keratinous substances are colored or dyed by being contacted with a mixture containing, as essential ingredients, an &#39;&#39;&#39;&#39;oxidation dye&#39;&#39;&#39;&#39; and either an ammonium or an alkali metal peroxydiphosphate; said &#39;&#39;&#39;&#39;oxidation dye&#39;&#39;&#39;&#39; is oxidized and condensed to a colored or natural appearing, substantially water-insoluble state in-situ and remains fixed within said hair or keratinous substance.

United States Patent Cohen et al.

[54] HAIR COLORING METHOD USING A PEROXYDIPHOSPHATE OXIDANT [72]Inventors: Bernard Cohen; Paul Raimond Mucenieks,

[21] Appl. No.: 733,830

[52] US. Cl ..8/10.2, 8/11, 8/32, 8/111, 424/62 [51] Int. Cl. ..A61k7/12 [58] Field of Search ..8/l0.2, 11, 32, l 1 1.5; 424/62 [56]References Cited UNITED STATES PATENTS 3,011,858 12/1961 Lantzet al..8/l0.2

3,167,478 1/1965 Charle et a1. ..8/10.2

3,218,234 11/1965 Wilmsmann et a1. ....424/62 X 3,378,444 4/1968 Swanson..424/62 1 1 Mar. 14, 1972 FOREIGN PATENTS OR APPLICATIONS 451,0266/1936 Great Britain ..8/l1 1.5 126,795 7/1928 Switzerland ..8/1 11OTHER PUBLICATIONS Hackh 5 Chemical Dictionary, 3rd Edition, TheBlakiston Company, Philadelphia, Pa., 1944), P. 634.

Primary Examiner-Albert T. Meyers Assistant Examiner-Vera C. ClarkeAttorney-Eugene G. Seems, Frank lanno and Milton Zucker ABSTRACT Hairand other keratinous substances are colored or dyed by being contactedwith a mixture containing, as essential ingredients, an oxidation dyeand either an ammonium or an alkali metal peroxydiphosphate; saidoxidation dye" is oxidized and condensed to a colored or naturalappearing, substantially water-insoluble state in-situ and remains fixedwithin said hair or keratinous substance.

6 Claims, No Drawings HAIR COLORING METHOD USING A PEROXYDIPHOSPHATEOXIDANT BACKGROUND OF THE INVENTION 1. Field of the Invention Thisinvention relates to improvements in the process and composition fordyeing human hair and other keratinous substances.

2. Description of the Prior Art It is known that human hair and otherkeratinous substances can be dyed or otherwise changed in color bytreating the hair with dye pigments which either coat the surface of thehair fibers or penetrate the hair fibers and form color particlestherein. While certain dyes can be used which merely coat the outside ofthe hair fibers, the most popular permanent dyeing processes are thosewhich utilize a so-called oxidation dye. These compounds are not in facttrue dyes, but dye precursors. They are aromatic organic compounds whichare converted to colored derivatives by oxidation, hence the termoxidation dyes; these compounds pass through an intermediate stage asimines or diimines and enter into condensation reactions to form larger,colored molecules.

These oxidation dyes" generally have the structure identified as inwhich R is an aromatic group which can have one, two or three aromaticrings condensed together and n is at least 1. These amino compounds mustbe easily oxidizable to imines and must be capable of condensing to formwater-insoluble, colored derivatives. A typical example of an oxidationdye" is p-phenylenediamine, and a typical reaction which converts thiscompound into a higher molecular weight colored molecule is set forthbelow:

HIN

After the stage of Bandronskys Base, further condensations can takeplace in a random way to give a large structure of the type:

In the application of the above type oxidation dye to human hair, thedye is mixed with a known oxidant, typically hydrogen peroxide, andimmediately applied to the hair fibers. The reaction between theoxidation dye" and the oxidant does not take place immediately, sincethe reaction proceeds at a relatively slow rate. During this period theoxidation dye" and the oxidant mixture thoroughly penetrate the hairfibers. The oxidation dye and the oxidant then progressively reactin-situ within the fiber, e.g., within the cortical layer of the hairfiber (or other keratinous fiber), to produce the xidized form of thedye. In this state, the dye quickly combines into large molecules of acolored dye by the condensation of a number of these molecules. Thecondensed, enlarged dye molecule, which now has the desired color, isthen trapped within the cortical layer of the hair fiber in the form ofan insoluble colored solid which cannot be easily removed from the hair.The entire oxidation and condensation reactions take place in from 15 toabout 30 minutes, and the excess dye and oxidant, e.g., hydrogenperoxide, are then washed from the hair, leaving the insoluble, coloreddye fixed within the hair or keratinous substance.

The most common oxidizing agent which is used in the above process ishydrpgen peroxide, although other oxidizing agents, such as ferricchloride, potassium dichromate and potassium permanganate, and the like,can be used. In many cases ammonium hydroxide is used as an alkalizeralong with the hydrogen peroxide to permit the oxidation reaction totake place within a desired pH range. The amount of hydrogen peroxideused must be sufficient to oxidize all the oxidizable groups on the dyemolecule.

The use of these dye compositions for coloring the hair has resulted inmany difficulties. One of these is that the oxidant which is used in thecomposition, normally hydrogen peroxide, does not imme;iately react withthe oxidation dye" and therefore is present on the hair in an uncombinedform. In this state the hydrogen peroxide can and does bleach hairfibers it contacts. This is undesired for a number of reasons.Initially, it lightens the hair and therefore makes the dyeing of thehair to a constant color difficult. Additionally, a portion of theperoxide is used up in bleaching the hair, rather than being utilizedfor its primary purpose of oxidizing the dye. The remaining peroxide maynot be sufficient to oxidize all of the dye to a proper shade or withinthe desired dyeing time.

Other difficulties are that the hydrogen peroxide must be used in verycontrolled, dilute solutions to avoid damaging the hair. Thus, sizableexcesses of peroxides must be avoided. Also, such oxidizing agents ashydrogen peroxide are relatively unstable and cannot be contained indilute solution for extended periods. Further, all of the knownoxidizing agents are relatively slow in reacting with oxidation dyes andtherefore require extended periods of time to complete the dyeingprocess.

OBJECTS OF THE INVENTION It is an object of the invention to prepare adyeing composition for dyeing hair and keratinous material with acomposition which does not attack or bleach the hair during the dyeingoperation.

It is a further object of the present invention to utilize a dyeingcomposition in which the oxidant components of the dye are stable ineither a dry or liquid state and which can be directly mixed with thedyeing composition prior to applica tion of the dyeing composition tothe hair.

It is still a further object of the present invention to utilize adyeing composition in which the oxidant can be used in highconcentration, without damaging the hair fibers, and in which the dyeingprocess is carried out in a shorter period of time than previouslypossible.

These and other objects will be apparent from the following descriptionof the invention.

SUMMARY OF THE INVENTION It has now been found that improved dyeing ofhair or keratinous materials can be carried out with a compositioncontaining an oxidation dye" and an oxidant in which the oxidantcontains, as an essential ingredient, either ammonium peroxydiphosphateor an alkali metal peroxydiphosphate.

DESCRIPTION OF THE INVENTION AND THE PREFERRED EMBODIMENTS In carryingout the present invention, one or more oxidation dyes is made up into anaqueous solution, containing from 1 to about 3 weight percent of thedye. In some cases the dyes are insoluble in water and a solvent whichis miscible with water must be used to obtain a water solution of thedyes. The term oxidation dye" as used in this application and in theclaims refers to those compounds having the structure wherein R is anaromatic group having from 1 to 3 aromatic rings and n is at least 1.Further, the aromatic groups can be unsubstituted or substituted withgroups such as, methyl, methoxy, sulfonate, sulfonic acid, nitro, ethyl,ethoxy, phenol, etc. These oxidation dyes also must have the property ofbeing readily oxidizable to imines and further must be capable ofcondensing into insoluble colored compounds having a higher averagemolecular weight than the nonoxidized precursor amines. Among theoxidation dyes which have been found suitable, are the following:p-aminodiphenylamine, paminophenylamine hydrochloride,p-aminodiphenylaminesulfonic acid, 2-amino-4-nitrophenol,4-amino-2-nitrophenol, o-aminophenol, p-aminophenol, p-aminophenolhydrochloride, p-aminophenol sulfate, 2-aminophenol-4-sulfonic acid,4-aminophenoI-2-sulfonic acid, N-(p-aminophenyl)glycine, o-anisidine,2,4-diaminoanisole, 2,4- diaminoanisole sulfate,p,p'-diaminodiphenylamine, p,p'- diaminodiphenyl aminesulfonic acid,p,p'-diaminodiphenyl methane, 1,8diaminonaphthalene,2,4-diaminophenetole, 2,4- diaminophenol, 2,4-diaminophenolhydrochloride, 2,5- diaminophenol-4-sulfonic acid,N,N-dimethyl-p-phenylenediamine, 4,6-dinitro2-aminophenol,N-(p-hydroxyphenyl)glycine, N-(Z-hydroxy-S-nitrophenyl)glycine,pmethylaminophenol sulfate, 4-nitro-o-phenylenediamine, 2-nitro-p-phenylenediamine, N-(p-nitrophenyl)glycine, o-phenylenediamine,m-phenylenediamine, m-phenylenediamine hydrochloride,p-phenylenediamine, p-phenylenediamine hydrochloride, p-phenylenediaminesulfate, mtolylenediamine, ptolylenediamine, 2,4,6-trinitroaniline.

In addition to the oxidation dyes many modifiers which are not aminesmay be used to modify and stabilize the shades obtained when the abovedyes are oxidized. Among these modifiers may be mentioned pyrocatechol,catechol( 1,2- dihydroxy benzene), resorcinol and pyrogallol. Othersinclude, for example, alpha and beta naphthols, diaminophenetole anddiamino-anisole. Many of these modifiers are essential in order toproduce the currently popular grayish tones, also termed silver, smoke,steel, etc., when these specific tones are desired. The dye formulationsalso may include antioxidants to prevent oxidation of the dyes due toatmospheric oxygen, and alkalizers to adjust the pH to those values inwhich the dyes operate best. Suitable alkalizers include sodiumcarbonate, ammonium hydroxide, ammonium bisulfite, etc.

In the present state of the art, the dye formulations normally contain amixture of several oxidation dyes and/or modifiers which are usedtogether to impart desirable highlights and/or shades to the basicoxidation dyes. These mixtures of dyes, and/or oxidants, and/ormodifiers are well known in the art and form no part of the instantinvention.

In accordance with the present invention, the above dye solution ismixed with an ammonium peroxydiphosphate or an alkali metalperoxydiphosphate, to form a thoroughly blended aqueous solution. Theperoxydiphosphate salts are added in effective amounts sufficient tooxidize all of the oxidizable groups contained in the dye. Normally atleast one mole of the peroxydiphosphate salt is necessary per mole ofoxidizable amino group in the dye. The peroxydiphosphate salt can beadded to the dye as an aqueous solution having a concentration of from1-30 percent by weight. In the makeup of the final dyeing solution, thedye materials can be mixed as a solid with the solid peroxydiphosphatesalts and both dissolved in water, or either of the components, i.e.,the dye materials or the peroxydisulfate, can be dissolved in water andthe other added thereto. In all events, the peroxydiphosphate oxidizerand the dye mixture must be in contact with each other in an aqueoussolution, in order to achieve proper dyeing of the hair or otherkeratinous material.

The solution of the peroxydiphosphate oxidizer and the dye componentsare then applied to hair or keratinous fibers and permitted to stand.The mixtures can be applied at any temperature from 32 to 212 F., butfor ease of application, room temperatures are normally employed. In thecase of dyeing human hair, the temperature of the final dyeing solutionshould be controlled so as not to injure the scalp tissues, e.g., 50 F.to F. is acceptable. The dye and peroxydiphosphate mixture is vigorouslyrubbed into the hair fibers so that both the peroxydiphosphate salt andthe dye component penetrate into the inner structure of the hair fibers,e.g., the cortical layer. Thereafter, the peroxydiphosphates commence tooxidize the dye components in-situ in the hair fibers. During thisoxidation the oxidation dye" is oxidized to the imine form and rapidlycommences to condense into larger molecules which give the desiredcolor. The color-forming, high-molecular weight molecules thus formedbecome fixed within the hair fibers because they are water-insoluble andbecause their large size traps them within the fibrous structure of thehair. In general, the rate at which color development commences isdependent upon the pH, and the higher the pH, i.e., the more alkalinethe solution, the slower is the rate of reaction and the emergence ofcolor.

The instant peroxydiphosphate salts can be used to oxidize dyecomponents in hair or keratinous materials at pHs ranging from 1 to l 1.However, in the process of bleaching human hair, the preferred pH of thedye solution should be maintained within 6 to 9 to avoid damage to thehair. In many instances, the optimum pH is dependent upon the solubilityof the dye material. Many are soluble only under alkaline or neutralconditions.

In the present process, the preferred alkali metal peroxydiphosphatesare the tetrasodium peroxydiphosphate, the tetrapotassiumperoxydiphosphate and protonated salts such as K H P O KI-I P O K HP ONa H P O NaH P o or Na HP O. No difference in the oxidizing ability hasbeen found between the potassium, sodium or ammonium peroxydiphosphatecompounds. All work equally well.

In the makeup of the dyeing solution, the peroxydiphosphate should beadded just prior to utilizing the dye solution for coloring hair,otherwise the peroxydiphosphate oxidizes the dye components prematurely.When this occurs, effective dyeing no longer can take place, since theoxidation and condensation of the dye molecule takes place outside ofthe hair fibers. If the resulting dye is applied to the hair, it willnot penetrate the hair fibers and yield a fast dye which cannot bewashed or rinsed out during normal shampooing.

In using the instant dyeing solution on hair, a water-soluble thickeneris generally added to the dyeing composition in order to obtain a thickconsistency for easy application to the hair. Among the suitablewater-soluble thickeners are compounds such as calcium carbonate,magnesium carbonate, Plaster of Paris and other inert fillers such astalc, kaolin and bentonite. A light magnesium carbonate has been foundmost suitable for this purpose. Other ingredients can also be used alongwith the thickeners to facilitate application, such as wetting agents,solvents, buffering agents, and the like. Optimum results have beenobtained when bleaching human hair with the present dyeing compositionwhen the pH is maintained between 5 and 9 and preferably at a pH rangeof about 7 to 8. The pH can be maintained by incorporating a suitablelevel of a buffering agent, for instance, a salt of a strong alkali anda weak acid. Among the buffering compounds which can be used areammonium bicarbonate, ammonium bisulfate, potassium hydrogen phthalate,tartaric acid, ammonium hydrogen tartrate and acid ammonium salts ofpolybasic inorganic and organic acids such as, for example, diammoniumphosphate.

In the present dyeing system, the use of buffers to adjust the pH isgenerally not necessary, since the added peroxydiphosphate oxidizersmaintain the pH within the range of 6 to 9. However, if added buffersare desired, these can be added to either raise or lower the pH of thedye composition to specified values.

mum-I rune 1n the above embodiment of the invention, the dye componentswere mixed with only a peroxydiphosphate salt in an aqueous solution andapplied to the hair just prior to dyeing. However, in another embodimentof the present invention, the oxidizer may contain a mixture of aperoxydiphosphate salt and a conventional oxidizing agent such ashydrogen peroxide or compounds that give off 11 0 in aqueous solution,e.g., alkali metal perborates such as sodium perborate, potassiumperborate, ammonium perborate, sodium carbonate peroxide, sodiumpyrophosphate peroxide, urea peroxide and melamine peroxide. Byutilizing these conventional oxidizers at low levels with aperoxydiphosphate, any bleaching or other attack on the hair by theseoxidizers is minimized. In all events, the oxidizing agent must contain,as an essential ingredient, either an ammonium or an alkali metalperoxydiphosphate in order to come within the purview of the presentinvention.

The present peroxydiphosphate compounds have many advantages over priorart oxidizers. Initially, they are most stable and can be handled assolids or in concentrated or dilute aqueous solutions withoutdecomposing on extended storage. Further, the peroxydiphosphate oxidizerpermits faster oxidation of the oxidation dyes than conventionaloxidizers, e.g., hydrogen peroxide. This permits the dyes to be set andthus form the desired colors in shorter periods of time. Mostimportantly, the present oxidizers operate well at low temperatures,particularly at normal ambient temperatures used in dyeing hair, i.e.,about 50 to about 100 F. Accordingly, no increase in the temperatures ofthe dyeing solution need be used to obtain a fast dye with the presentoxidizing system.

Of particular importance in the present dyeing application is the factthat the peroxydiphosphate compounds when used as oxidizers do notattack hair or degrade it in any way, even in high concentrations. Thisis considered most unusual, since H 0 and other peroxygen oxidizersnormally cause some undesired degradation of the hair during the dyeingprocess. The present peroxydiphosphate oxidizer is most selective inthat it permits better dyeing in shorter amounts of time with noincrease in the attack on the hair fibers. Also, the peroxydiphosphatesare not toxic, and no special handling problems present themselves inthe use of these oxidizer compositions.

Another advantage of the present oxidizers is that they can be mixeddirectly with a dye composition in a dry form and can remain standingfor limited periods without substantially reacting with the dyes.Thereafter, in order to use the dyeing composition, water is addedthereto to dissolve the ingredients, and the composition is thenimmediately applied to the hair.

The following examples are given to illustrate the present invention andare not deemed to be limiting thereof.

EXAMPLE 1 A 3 percent aqueous solution of a medium brown dye base wasmade up consisting of the following:

Ingredients I: by Weight p-phenylenediamine 2.00 p-aminodiphenylamine0.16 o aminophenol 0.25 4-nitro-l,Z-diaminobenzene 0.20 Resorcinol 1.50Ammonium hydroxide q.s. (to pH Sodium sulfite q.s. (to stabilize dyes)Dye base, to make 10000 with water for several minutes. The color in thelock of hair was found to be fast and not altered in intensity or lusterby the water washing.

EXAMPLE 2 Three grams of the dye mixtures set forth in Example 1, butwithout the ammonium hydroxide, was mixed with 30 grams oftetrapotassium peroxydiphosphate (14,150,). The two solids werethoroughly blended together and then dissolved in sufficient water togive a 1.5 percent dye concentration having a pH of 7.0. The resultingmixture was then immediately applied to a lock of brown-gray hair as setforth in Example l. The color was found to be fast and substantially thesame as that set forth in Example 1.

EXAMPLE 3 The process of Example 1 was repeated on wool and muskrat fursamples and similar fast dyeing was obtained. No significant differencesin the rate of color development were noted.

EXAMPLE 4 The procedure of Example 3 was repeated except that thesesamples each were dyed with dyeing solution having pH values of 1.6, 7.2and 1 1.2, respectively. Dyeing with these solutions resulted in thesame color as that set forth in Example 3 except that the developmenttime was decreased to as little as 5 minutes when dyeing was carried outat a pH of 1.6.

EXAMPLE 5 The procedure of Example 1 was repeated except that in placeof the tetrapotassium peroxydiphosphate the equivalent sodium andammonium salts of the peroxydiphosphate were used. The resulting hairsamples showed the same color development and color shade as thatobtained in Example 1 when the tetrapotassium peroxydiphosphate wasutilized.

EXAMPLE 6 A dye formulation was made up containing the following;

Ingredients 1: by Weight p-phenylenediamine 1.70 2,4-diarninoanisole0.60 4-arnino-2-nitrophenol 0.12 p-aminophenol 0.15Z-niIm-pphenylenediamine 0.05 Pyrogallol 0.30 Resorcinol 1.70 Ammoniumhydroxide q.s. (pH 10) Sodium sull'lte q.s. (to stabilize dyes) DyeBase. to make 100.00

EXAMPLE 7 Example 6 was repeated using 0.1 percent of a wetting agent,Triton X-lOO (alkyl phenoxy polyethoxy ethanol) supplied by Rohm andHaas Company. The results were equivalent to that set forth in Example6, except that the wetting agent allowed easier application of theperoxydiphosphate solution.

EXAMPLE 8 The procedure of Example 7 was repeated except that 0.2percent of hydroxyethyl cellulose was used as a thickening agent.The'results were the same as obtained in Example 7, except that thethickening agent allowed easier application of the dyeing solution. I

EXAMPLE 9 EXAMPLE 10 The procedure of Example 6 was repeated usingpercent sodium perborate monohydrate mixed with 5 percent tetrapotassiumperoxydiphosphate. The results were substantially the same as thoseobtained in Example 6. Further, no noticeable degradation of the hairresulted from the use of this oxidation mixture.

Pursuant to the requirements of the Patent Statutes, the principle ofthis invention has been explained and exemplified in a manner so that itcan be readily practiced by those skilled in the art, suchexemplification including what is considered to represent the bestembodiment of the invention. However, it should be clearly understoodthat, within the scope of the appended claims, the invention may bepracticed by those skilled in the art, and having the benefit of thisdisclosure otherwise than as specifically described and exemplifiedherein.

What is claimed is:

1. In the process of coloring a member selected from the groupconsisting of human hair and keratinous fibers by contacting said memberwith a composition containing as essential ingredients, an oxidation dyeand an oxidant for said dye in an aqueous medium, the improvement whichcomprises using as said oxidant an effective amount of a member selectedfrom the group consisting of ammonium peroxydiphosphate and an alkalimetal peroxydiphosphate.

2. Process of claim 1 wherein said alkali metal peroxydiphosphate istetrapotassium peroxydiphosphate 3. Process of claim 1 wherein saidalkali metal peroxydiphosphate is tetrasodium peroxydiphosphate.

4. Process of claim 1 wherein the peroxydiphosphate oxidant is presentin said composition in amounts sufficient to have at least 1 mole ofsaid peroxydiphosphate oxidant per mole of oxidizable amine grouppresent in said dye.

5. Process of claim 1 wherein the peroxydiphosphate oxidant is presentwithin said composition as an aqueous solution containing from about ito about 30 weight percent of said peroxydiphosphate oxidant.

6. In the process of coloring a member selected from the groupconsisting of human hair and keratinous fibers by contacting said memberwith a composition containing as essential ingredients, an oxidation dyeand an oxidant for said dye in an aqueous medium, the improvement whichcomprises using as said oxidant an effective amount of a member selectedfrom the group consisting of ammonium peroxydiphosphate and an alkalimetal peroxydiphosphate, and a peroxygen compound selected from thegroup consisting of hydrogen peroxide and an alkali metal perborate.

2. Process of claim 1 wherein said alkali metal peroxydiphosphate istetrapotassium peroxydiphosphate.
 3. Process of claim 1 wherein saidalkali metal peroxydiphosphate is tetrasodium peroxydiphosphate. 4.Process of claim 1 wherein the peroxydiphosphate oxidant is present insaid composition in amounts sufficient to have at least 1 mole of saidperoxydiphosphate oxidant per mole of oxidizable amine group present insaid dye.
 5. Process of claim 1 wherein the peroxydiphosphate oxidant ispresent within said composition as an aqueous solution containing fromabout 1 to about 30 weight percent of said peroxydiphosphate oxidant. 6.In the process of coloring a member selected from the group consistingof human hair and keratinous fibers by contacting said member with acomposition containing as essential ingredients, an oxidation dye and anoxidant for said dye in an aqueous medium, the improvement whichcomprises using as said oxidant an effective amount of a member selectedfrom the group consisting of ammonium peroxydiphosphate and an alkalimetal peroxydiphosphate, and a peroxygen compound selected from thegroup consisting of hydrogen peroxide and an alkali metal perborate.